KR102602088B1 - Dental cement composition and method of use - Google Patents

Abstract

Provided herein are dental compositions and methods of use in dental cementation applications.

Description

Dental cement composition and method of use

The field of use is useful in dental compositions, especially dental cementation applications.

Dental restorative material or dental filling material is a dental restorative material used to restore the function, integrity, and morphological structure of lost tooth structure. Loss of structure is usually due to caries or trauma (collectively referred to herein as cavities). It may be intentionally lost during tooth preparation to improve the aesthetic or physical integrity of the intended restorative material.

Dental cements are used in a variety of dental and orthodontic applications, including use as sealing agents, pulp-protectors, or cavity-lining materials. Additionally, it is used to protect the dental pulp from damage by forming an insulating layer beneath metal, resin or ceramic restorations. This helps seal or secure and cast an inlay, onlay, or any such material to both dentin and enamel.

Resin cements usually fall into two categories: total-etch and self-adhesive resin cements. For proper use, pure resin cements require pretreatment of the tooth surface, preferably by application of phosphoric acid and dentin and enamel primers, prior to application of the resin cement. After curing, it forms a micromechanical bond to both dentin and enamel. Additionally, it is insoluble in oral fluid. There are two types of these "conventional resin cements" (those requiring the use of "blanket-etch technology and dentin adhesive technology") that are commonly used - double-cured and light-cured versions. The most recent member of the "resin cement family" is a self-retaining cement that does not require pretreatment of the tooth surface and appears to have many of the clinical advantages of conventional resin cement systems with the ease of use of more classic types of cement. It is an adhesive resin cement. It is important to note that, in general, the bond strength of self-eroding resin cements is not as high as that in resin cements using gross-eroding techniques and may consequently be more likely to lead to microleakage at the edges.

An ideal dental cementation material can provide strong, durable cementation and ease of use.

[Summary of invention]

In certain embodiments, provided herein are dental compositions comprising a polymerizable monomer and a hydroperoxide and/or thiourea. In some embodiments, the composition further includes copper(II) (e.g., as a catalyst).

Also provided herein is a dental composition, the composition comprising a binder and a paste mixture on the surface of a dental substrate, wherein the binder comprises at least one phosphoric acid-containing (meth)acrylic monomer, and the paste mixture comprises: It includes at least one polymerizable monomer, at least one hydroperoxide, and at least one thiourea compound. The phosphoric acid-containing (meth)acrylic monomers include GPDM (glycerol phosphate di(meth)acrylate {(meth)acrylate = acrylate or methacrylate}), phenyl-P (phenyl methacryloxyethyl phosphate), and PENTA-P. (Dipentaerythritol pentaacrylate phosphate), 10-MDP (methacryloyloxydecyl phosphate), HEMA-P (hydroxyethyl methacrylate phosphate), HEA-P (hydroxyethyl acrylate phosphate), bis. (HEMA)-P {bis(hydroxyethyl methacrylate) phosphate), bis(HEA)-P {bis(hydroxyethyl acrylate) phosphate), bis((meth)acryloxypropyl) phosphate and combinations thereof. is selected from the group consisting of In a specific embodiment, the phosphoric acid containing (meth)acrylic monomer is 10-methacryloyloxydecyl dihydrogen phosphate (10-MDP). The thiourea is 1-(2-pyridyl)-2-thiourea (PTU), 1-benzoyl-2-thiourea (BTU), 1-acetyl-2-thiourea (ATU), 1-(2- It is selected from the group consisting of tetrahydrofurfuryl)-2-thiourea (TTU) or a combination thereof. In a specific embodiment, the thiourea is 1-(2-pyridyl)-2-thiourea (PTU). In a specific embodiment, the hydroperoxide is a tertiary hydroperoxide. In specific embodiments, either the first portion or the second portion of the paste mixture further comprises a copper(II) compound. In a specific embodiment, the dental substrate is zirconia. In another embodiment, the bonding agent is a single bottle bonding agent.

Also provided herein is a method of tooth restoration, the method comprising: applying a dental bonding agent on a dental substrate, wherein the bonding agent comprises at least one phosphoric acid-containing (meth)acrylic monomer. A first step; and applying the paste mixture from a device comprising a first portion and a second portion that are separate from each other, wherein the first portion and the second portion form a paste mixture, and the paste mixture from the device is applied to the first portion. A second step comprising at least one polymerizable monomer and at least one hydroperoxide and in the second part at least one thiourea compound. In a specific embodiment, the phosphoric acid containing (meth)acrylic monomer is GPDM (glycerol phosphate di(meth)acrylate {(meth)acrylate = acrylate or methacrylate}), phenyl-P (phenyl methacryloxyethyl phosphate) ), PENTA-P (dipentaerythritol pentaacrylate phosphate), 10-MDP (methacryloyloxydecyl phosphate), HEMA-P (hydroxyethyl methacrylate phosphate), HEA-P (hydroxyethyl acrylate) late phosphate), bis(HEMA)-P {bis(hydroxyethyl methacrylate) phosphate), bis(HEA)-P {bis(hydroxyethyl acrylate) phosphate), bis((meth)acryloxypropyl) It is selected from the group consisting of phosphate and combinations thereof. In a specific embodiment, the phosphoric acid containing (meth)acrylic monomer is 10-methacryloyloxydecyl dihydrogen phosphate (10-MDP). The thiourea is 1-(2-pyridyl)-2-thiourea (PTU), 1-benzoyl-2-thiourea (BTU), 1-acetyl-2-thiourea (ATU), 1-(2- It is selected from the group consisting of tetrahydrofurfuryl)-2-thiourea (TTU) or a combination thereof. In a specific embodiment, the thiourea is 1-(2-pyridyl)-2-thiourea (PTU). In a specific embodiment, the hydroperoxide is a tertiary hydroperoxide. In specific embodiments, either the first portion or the second portion of the paste mixture further comprises a copper(II) compound. The binder effectively binds to the dental substrate. In a specific embodiment, the dental substrate is zirconia. In specific embodiments, the bonding strength of the dental bonding agent on the dental substrate exceeds 15 MPa. In one embodiment, the device is a double-barrel syringe.

Also provided is a dental composition, the composition comprising a binder and a paste mixture on the surface of a dental substrate, wherein the binder comprises at least one phosphoric acid-containing (meth)acrylic monomer, and the paste mixture is is formed by mixing together a previously separated first portion and a second portion, wherein the first portion comprises at least one polymerizable monomer and at least one hydroperoxide, and the second portion comprises at least one hydroperoxide. Includes species of thiourea compounds. In a specific embodiment, the previously separate first and second portions are separate in a double-barrel syringe.

In another embodiment, the dental composition includes a first part and a second part, wherein the first part comprises a copper(II) catalyst, a hydroperoxide, and a polymerizable monomer, wherein the polymerizable monomer has an ethylene-based group. and the second portion includes a copper(II) catalyst, thiourea, and a polymerizable monomer, wherein the polymerizable monomer includes an ethylene-based group. In specific embodiments, the first portion and the second portion are physically separated (e.g., to the point where the dental composition is used to restore a cavity of a tooth).

In some embodiments, provided herein is a dental composition comprising a first and a second part, the first and second parts collectively comprising: a copper(II) catalyst; hydroperoxide; Polymerizable monomers containing ethylene-based groups; and thiourea. In a specific embodiment, the first portion comprises hydrogen peroxide, the second portion comprises thiourea, and the first and second portions (e.g., a dental composition used to restore a cavity of a tooth) (up to the point where they are physically separated from each other).

In some embodiments, provided herein is a dental composition, a portion thereof, or a resin precursor thereof, the composition comprising: a copper(II) catalyst; hydroperoxide; and polymerizable monomers (such as polymerizable monomers containing ethylene-based groups). Likewise, in certain embodiments, provided herein is a dental composition, a portion thereof, or a resin precursor thereof, the composition comprising: a copper(II) catalyst; thiourea; and polymerizable monomers (such as polymerizable monomers containing ethylene-based groups).

In some embodiments, provided herein is a dental composition (e.g., a quick cure copper-free acid-free composition) comprising a first and a second part, the first and second parts collectively comprising: Peroxides (e.g. hydroperoxides are tertiary aryl hydroperoxides (e.g. HOOCR' ₃ where each R' is independently alkyl or aryl and at least one R' is an aryl (e.g. substituted or unsubstituted aryl)) , such as cumene hydroperoxide); polymerizable monomers (such as polymerizable monomers containing ethylene-based groups); and thiourea. In some embodiments, the first portion comprises hydrogen peroxide and the second portion comprises thiourea, and the first and second portions are physically separated from each other. In specific embodiments, the hydroperoxide has a concentration in the dental composition of at least about 1.5% (w/w), or relative to monomer, at least about 1.5% (w/w). In a more specific embodiment, the hydroperoxide has a concentration in the dental composition of at least about 2% (w/w), or relative to the monomer, at least about 2% (w/w). In a more specific embodiment, the hydroperoxide has a concentration in the dental composition of at least about 2.5% (w/w), or relative to the monomer, at least about 2.5% (w/w). In additional or alternative embodiments, the thiourea has a concentration in the dental composition of at least about 1.5% (w/w), or at a concentration relative to monomer of at least about 1.5% (w/w). In a more specific embodiment, the thiourea has a concentration in the dental composition of at least about 2% (w/w), or at a concentration relative to monomer of at least about 2% (w/w). In a more specific embodiment, the thiourea has a concentration in the dental composition of at least about 2.5% (w/w), or at a concentration relative to monomer of at least about 2.5% (w/w). In a further or additional embodiment, the combined weight of hydroperoxide plus thiourea has a concentration in the dental composition of at least about 3% (w/w), or a concentration relative to monomer of at least about 3% (w/w). In a more specific embodiment, the combined weight of hydroperoxide plus thiourea has a concentration in the dental composition of at least about 4% (w/w), or a concentration relative to monomer of at least about 4% (w/w). In a more specific embodiment, the combined weight of hydroperoxide plus thiourea has a concentration in the dental composition of at least about 5% (w/w), or a concentration relative to monomer of at least about 5% (w/w).

In certain embodiments, the copper(II) catalyst comprises copper(II) ions and/or copper(II) compounds. In specific embodiments, the copper(II) catalyst comprises copper(II) sulfate, copper(II) acetate, copper(II) chloride, copper(II) acetylacetonate, or combinations thereof. In some embodiments, the copper(II) catalyst is present in the composition in an amount of up to about 5% by weight (such as up to about 1% by weight or up to about 0.1% by weight).

In some embodiments, hydroperoxides include hydrocarbons (such as C ₄ -C ₂₀ hydrocarbons) substituted with one or more -OOH groups. In specific embodiments, the hydroperoxide is a tertiary hydroperoxide (e.g., the -OOH group is substituted with a carbon bearing a tertiary substitution). In a more specific embodiment, the hydroperoxide is t-butyl hydroperoxide, t-amyl hydroperoxide, p-diisopropylbenzene hydroperoxide, cumene hydroperoxide, pynanhydroperoxide, p-methane hydroperoxide. and 1,1,3,3-tetramethylbutyl hydroperoxide, or a combination thereof. In additional or alternative embodiments, the hydroperoxide is present in the composition in an amount from about 0.01% (w/w) to about 10% (w/w). In a more specific embodiment, the hydroperoxide is present in the composition in an amount of about 0.1% (w/w) to about 5% (w/w). In some embodiments, the hydroperoxide is present in the composition at a hydroperoxide to polymerizable monomer ratio of about 1:9999 to about 1:9. In a more specific embodiment, the ratio of hydroperoxide to polymerizable monomer is from about 1:99 to about 5:95.

In certain embodiments, the monomer is a dentally acceptable monomer. In some embodiments, the monomer includes vinyl, acrylate, methacrylate, or combinations thereof. In additional or alternative embodiments, the monomer is present in an amount from about 10% (w/w) to about 60% (w/w). In a more specific embodiment, the polymerizable monomer is present in an amount of about 20% (w/w) to about 50% (w/w).

In certain embodiments, the thiourea is 1-(2-pyridyl)-2-thiourea (PTU), 1-benzoyl-2-thiourea (BTU), 1-acetyl-2-thiourea (ATU), 1 -(2-tetrahydrofurfuryl)-2-thiourea (TTU) or a combination thereof. In a further or alternative embodiment, the thiourea is present in the composition in a thiourea to polymerizable monomer ratio of about 1:999 to about 100:900. In a more specific embodiment, the ratio of thiourea to polymerizable monomer is from about 1:99 to about 10:90.

In specific embodiments, the dental compositions provided herein include fillings. In a more specific embodiment, the first and second portions include filler. In an even more specific embodiment, the filler is a finely divided filler. In some embodiments, the finely divided filler comprises a plurality of particles. In specific embodiments, the particles have an average dimension (eg, diameter) of about 0.02 micrometers to about 30 micrometers, such as about 0.2 micrometers to about 10 micrometers. In additional or alternative embodiments, the filler includes an inorganic filler, a pre-polymerized filler, or a combination thereof. Fillers include, but are not limited to, metal oxides, metal nitrides, metal fluorides, silicates, silica (e.g. colloidal silica, precipitated silica, fused silica), aluminosilicates, aluminoborosilicates, fluoroalumines. Nosilicate, Barium Silicate, Barium Aluminosilicate, Barium Aluminoborosilicate, Strontium Aluminosilicate, Barium Fluoroaluminosilicate, Strontium Fluoroaluminosilicate, Strontium Zinc Fluoroaluminosilicate, Zinc Aluminosilicate, Dictionary -Polymeric fillers and combinations thereof are included. In some embodiments, the filler is present in an amount from about 10% (w/w) to about 90% (w/w). In a more specific embodiment, the filler is present in an amount of about 40% (w/w) to about 80% (w/w). In an even more specific embodiment, the filler is present in an amount of about 60% (w/w) to about 80% (w/w).

In some embodiments, the composition includes a photoinitiator, stabilizer, solvent, or any combination thereof. In some embodiments, the photoinitiator is present in an amount of about 5% (w/w) or less. In additional or alternative embodiments, the stabilizer is present in an amount of about 1% (w/w) or less.

In some embodiments, the compositions provided herein are free or substantially free of acids or anhydrides. In specific embodiments, the composition (and/or portion(s) thereof) contains less than 5% (w/w) acid (e.g., less than 3% (w/w), less than 1% (w/w), or 0.5% (w/w) w/w) or less). In specific embodiments, the composition or portion thereof is non-acidic (e.g., has a pH of about 5 or greater).

In various embodiments, the compositions provided herein have excellent performance characteristics, such as when used in restorative dental applications (such as restoring teeth with Class I or Class II cavities). In specific embodiments, upon combining the first and second portions, the total volume of the composition (such as when it is cured) is reduced by less than 10% (such as less than 8%, less than 6%, or less than 4%). In some cases, minimizing such shrinkage reduces the incidence of void formation between the filling and the tooth, reduces the incidence of tooth damage (e.g. cracking) during and after restoration, and the like. In a further or alternative embodiment, when combining the first and second parts, the hygroscopicity of the composite is less than 100 μg/mm ³ (e.g. less than 50 μg/mm ³ , less than 25 μg/mm ³ , less than 20 μg/mm ³ or less than 15 μg/mm ³ ). In some cases, minimizing hygroscopicity leads to composites that can reduce expansion of the restorative material after hardening, thereby reducing the incidence of tooth damage (e.g. cracking), build-up of filling material from the tooth, etc.

Also provided herein are dental composites resulting from mixing components or parts of the compositions described herein, such as partially or fully cured mixtures. In some embodiments, the composite includes partially or fully cured resin, filler, and copper. In a specific embodiment, the composite material comprises cured resin in an amount of about 10% (w/w) to about 60% (w/w), filler in an amount of about 10% (w/w) to about 90% (w/w). , and copper in an amount of up to about 1 elemental weight percent. Also provided herein is a reaction mixture comprising a copper(II) catalyst, a hydroperoxide, a polymerizable monomer, a polymerizable monomer comprising an ethylene-based group, and a thiourea. The reaction mixture can be partially cured by having some of its monomer units forming monomers and other portions forming oligomers or polymers thereof.

In some embodiments, the two-part compositions provided herein are contained within a dual chamber device comprising a housing body, the housing body comprising a first chamber and a second chamber, the first chamber as described herein. and the second chamber contains a second portion of the composition described herein. In specific embodiments, the dual chamber device is configured to simultaneously extrude and/or mix the first and second portions.

Also provided herein are methods of restoration of teeth in a subject. In some embodiments, the method combines a first composition (e.g., a first portion of a dental composition described herein) with a second composition (e.g., a second portion of a dental composition described herein) to form a mixed composition. Includes ordering. In specific embodiments, the first composition comprises a hydroperoxide, the second composition comprises a thiourea, and one or both of the first and/or second compositions include a copper(II) catalyst, a polymerizable monomer, and (such as polymerizable monomers containing ethylene groups) and fillers. In some embodiments, the method further comprises administering the mixed composition to the subject (e.g., to a Class I or Class II cavity of the subject's tooth). In some embodiments, the method further comprises curing the mixed composition (e.g., allowing the composition to self-cure and/or using a dental curing light to light-cure the composition). In specific embodiments, curing of the mixed composition leads to the formation of a restorative composite (e.g., in the form of a filling within a subject's dental cavity). In a preferred embodiment, the curing step (eg self-curing) occurs relatively quickly to facilitate the restoration process. In specific embodiments, the curing step (e.g., self-curing or coagulation) occurs within 10 minutes, within 4 minutes, within 2 minutes, etc.

In a specific embodiment, the method of the invention comprises the following steps: 1) applying a dental bonding primer onto dentin and enamel (e.g. tooth structure), optionally followed by applying a cure activator, optionally applying a dental bonding primer; curing the primer layer using a curing light; 2) This is a step of applying a dental bonding primer to prefabricated restoration materials such as crowns, inlays, onlays, and veneers, and optionally subsequently applying a curing activator, optionally using a dental curing light. curing the primer layer; 3) Bonding the prefabricated restoration to the tooth structure (dentin and enamel) by applying a layer of dental cement.

In some embodiments, the method includes removing decay from within and around the cavity to be filled (e.g., drilling the tooth to remove decay therefrom).

In view of the following detailed description and appended claims, with reference to the accompanying drawings, all of which form a part of this specification, the compositions disclosed herein, parts thereof, precursors thereof, resulting composites and methods as well as methods of making these and Other purposes, characteristics and characteristics will be revealed further. However, it should be explicitly understood that the drawings are for illustration and explanation purposes only and are not intended to limit the scope of the present invention. As used in the specification and claims, the singular forms include plural references unless the context clearly dictates otherwise.

Provided herein are dental compositions. Also provided herein are component parts thereof, methods of tooth restoration, resins used in the manufacture of dental compositions, dental composites (such as filling materials), and the like. In a specific embodiment, the dental composition comprises two parts, such that the two parts remain physically separate from each other. In some instances, when the two parts are combined, such as when the dental composition is used in a tooth restoration method (such as that described herein), the composition forms a composite (such as a filling material used in tooth restoration). .

In specific embodiments, provided herein are dental compositions comprising two parts, such as when mixing them initiates free radical polymerization, and in some embodiments the two part dental compositions comprise: (1) at least one monomer having at least one ethylenically unsaturated group (e.g., as described herein, also referred to herein as a polymerizable monomer containing an ethylenically unsaturated group); (2) a portion comprising at least one hydroperoxide group; and (3) a portion comprising at least one substituted thiourea. In a more specific embodiment, the two-part dental composition comprises: (1) at least one monomer having at least one ethylenically unsaturated group; (2) a portion comprising at least one hydroperoxide group; (3) a portion comprising at least one substituted thiourea; (4) at least one copper(II) compound (e.g., copper(II) that promotes, e.g., facilitates and/or accelerates, the curing of the composition (e.g., the polymerization of its monomer components) when combining the first and second parts. at least a portion comprising a compound).

In specific embodiments, provided herein comprises first and second parts, wherein the first part includes (1) a copper(II) catalyst; (2) hydroperoxide; and (3) a polymerizable monomer comprising an ethylene-based group, the second portion comprising (1) a copper(II) catalyst; (2) thiourea; and (3) a polymerizable monomer containing an ethylene-based group. Also provided herein are, for example, (1) copper(II) catalysts; (2) hydroperoxide; and (3) a polymerizable monomer comprising an ethylene-based group, and/or (1) a copper(II) catalyst; (2) thiourea; and (3) a dental composition comprising a polymerizable monomer comprising an ethylene-based group.

In certain embodiments, provided herein includes a housing body, the housing body comprising a first chamber and a second chamber, the first chamber containing therein a first portion of the composition described herein; , the second chamber is a dual chamber device containing therein a second portion of the composition provided herein. In some embodiments, the dual chamber device is suitable for simultaneously extruding the first and second portions, such as to enable mixing of the first and second portions and to promote initiation and polymerization of their monomer component(s). Any suitable device. In a specific embodiment, the dual chamber device is a double barrel syringe comprising a nozzle configured to promote mixing of first and second portions upon (simultaneous) descent including first and second plungers.

In certain embodiments, the monomer having at least one ethylenically unsaturated group or the polymerizable monomer comprising an ethylenically group is a compound comprising at least one >C=C< group. In specific embodiments, the monomers are represented by the formula R ₂ C=CR ₂ , wherein each R is independently selected from H, COOR ¹ or an optionally substituted hydrocarbon, such as alkyl, aryl, etc., such that at least one R is It's not H. In specific embodiments, at least one R is COOR ¹ or aryl (such as phenyl, etc.). In some embodiments, R ¹ is either H or alkyl (eg C ₁ -C ₆ alkyl). In a more specific embodiment, alkyl is C ₁ -C ₆ alkyl (eg, methyl, ethyl, etc.). In certain embodiments, the alkyl is acyclic (eg, branched or straight chain) or cyclic, saturated or unsaturated alkyl. In some embodiments, optional substituents include, but are not limited to, -OH, alkyl, and/or aryl. In certain embodiments, the monomer comprises one or more moieties represented by the formula R ₂ C=CRL, wherein the R and L groups are independently as described for the R group above. In certain embodiments, the monomer comprises two or more R ₂ C=CRL groups, where the L groups are linked to each other as shown in Formula I below (e.g., as R ₂ C=CRL-(LCR=CR ₂ ) _a , where a>0, e.g. 1-5, e.g. 1-2):

(I)

For example, in some embodiments, the monomer is optionally R ₂ C=CR-COO((CH ₂ ) _m (CHOH) _n ) _p OOC-RC=CR ₂ , where m is 1-6 (e.g. 2-4 ), n is 0-1, and p is 1-30 (eg 1-10).

In specific embodiments, the monomers are acrylates (e.g. three R groups = H and one R group = COOR ¹ ), methacrylates (e.g. two R groups = H and one R group = methyl, Another R group (on the same carbon as methyl is COOR ¹ ) or a vinyl group (at least one R group is a hydrocarbon). In some embodiments, the monomer includes acrylate, methacrylate, and/or vinyl groups. In specific embodiments, the ethylenically unsaturated group is selected from acrylate and methacrylate groups. Examples of polymerizable monomers include, but are not limited to: glycerol di(meth)acrylate, glycerol mono(meth)acrylate, hydroxyethyl (meth)acrylate {(meth)acrylate = acrylate or is methacrylate}, hydroxypropyl (meth)acrylate, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, octyl (meth)acrylate, decyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2'-ethoxy-2-ethoxyethyl (meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol Di(meth)acrylate, polyethylene glycol mono-(meth)acrylate, polyethylene glycol di-(meth)acrylate, polypropylene glycol mono-(meth)acrylate, polypropylene glycol di-(meth)acrylate, poly Tetramethylene glycol mono-(meth)acrylate, polytetramethylene glycol di-(meth)acrylate, hexanediol di(meth)acrylate, octanediol di(meth)acrylate, decanediol di(meth)acrylate, Trimethyloylpropane tri(meth)acrylate, urethane dimethacrylate (reaction adduct of 2-hydroxyethyl methacrylate with 2,4,4-trimethylhexane diisocyanate), 2,2-bis[4 -(2-hydroxy-3-methacryloylpropoxy)-phenyl]-propane (bis-GMA), ethoxylated bisphenol A dimethacrylate in tetrahydrofurfuryl (meth)acrylate (ethylene oxide in molecule) The total number of moles of seeds may range from 2 to 30 units) or mixtures thereof. When referred to herein, “(meth)acrylate” includes disclosures of both methacrylates and acrylates.

In certain embodiments, the amount of monomer present in the composition is any suitable amount. In certain embodiments, the dental compositions provided herein include monomers in a weight percentage amount (e.g., of the total composition) between 10% and 60%. In a more specific embodiment, the weight percentage is between 20% and 50%.

In certain embodiments, the compositions provided herein include copper(II), such as in the form of a copper(II) compound. In specific embodiments, copper(II) (e.g., a copper(II) compound) is used to catalyze curing (e.g., solidification or other coagulation) of the composition (e.g., to accelerate or otherwise promote polymerization of monomers). It is used. In a specific example, when two parts of the composition of the present invention are mixed, the presence of copper(II) (e.g., a compound thereof) accelerates the polymerization process (e.g., whereby the hydroperoxide and thiourea that were separated are combined). and the initiation of polymerization is promoted, which is accelerated by the presence of copper(II)). The copper(II) catalyst optionally exists in dissociated, bound (e.g., in the form of a copper(II) compound), or partially bound form. In various embodiments, the copper(II) compound is any suitable compound that includes at least one copper(II) in its molecular formula. Examples of copper(II) compounds include, but are not limited to, copper(II) sulfate, copper(II) acetate, copper(II) chloride, copper(II) acetylacetonate, and combinations thereof. In a specific embodiment, the copper(II) compound is copper(II) acetate. In another embodiment, the copper(II) compound is copper(II) acetylacetonate. In specific embodiments, the weight percentage of copper(II) (or a compound thereof) is less than 1%. In a more specific embodiment, the weight percentage of copper(II) (or a compound thereof) is less than 0.1%. In an even more specific embodiment, copper(II) (or a compound thereof) is provided in, or combined with, the compositions herein in an amount of from about 0.001% to about 0.05% by weight.

In certain embodiments, the hydroperoxide is any suitable agent, such as when combined with the thiourea provided herein, that initiates and/or otherwise promotes polymerization of the monomers herein at a rate suitable for dental applications, especially restorative applications, It is an agent specifically approved for dental use. In some embodiments, the hydroperoxide is represented by the formula HOO-R ² , where R ² is any suitable organic group. In specific embodiments, R ² is a hydrocarbon, such as a C ₄ -C ₂₀ hydrocarbon (optionally substituted by any suitable group, such as an alkyl group, an aryl group (such as phenyl), an alkylaryl group, an additional -OOH group, etc. In some embodiments, R ² is represented by the formula -CR ³ R ⁴ R ⁵ , where R ³ , R ⁴ and R ⁵ are each independently selected from H, alkyl (cyclic and/or acyclic, and branched or straight chain) ), aryl (e.g. phenyl), arylalkyl (e.g. alkyl bonded to carbon), alkylarylalkyl, etc., wherein the group is optionally substituted or unsubstituted. In some embodiments, at least two of R ³ , R ⁴ and R ⁵ are not H. In a specific embodiment, the hydroperoxide is a tertiary hydroperoxide, that is, none of R ³ , R ⁴ and R ⁵ is H. In certain cases, any one or more of R ³ , R ⁴ and/or R ⁵ is optionally combined with another or both of R ³ , R ⁴ and R ⁵ to form a cyclic (mono- or polycyclic) alkyl group. (optionally substituted or unsubstituted as discussed herein). As discussed herein, any suitable hydroperoxide compound having at least one hydroperoxide group is optionally used. In specific embodiments, the hydroperoxide compound includes more than one hydroperoxide group. Non-limiting examples of hydroperoxide compounds include t-butyl hydroperoxide, t-amyl hydroperoxide, p-diisopropylbenzene hydroperoxide, cumene hydroperoxide, pynanhydroperoxide, p-methane hydroperoxide. and 1,1,3,3-tetramethylbutyl hydroperoxide, but are not limited thereto.

In some embodiments, any suitable hydroperoxide concentration is optionally used in the compositions and methods provided herein. In specific embodiments, the total hydroperoxide compound(s) is present in a range of about 0.01% (w/w) to about 10.0% (w/w) (e.g., of the total composition). In certain embodiments, the hydroperoxide is present in a range from about 0.1% (w/w) to about 5.0% (w/w) of the total composition. In some embodiments, the hydroperoxide is present in the composition in an amount of about 1.5% (w/w) to about 5% (w/w). In certain cases, the hydroperoxides provided herein, such as those specifically mentioned above, are stable under a variety of conditions and have a long shelf life.

Any suitable thiourea is optionally used in the compositions described herein (such as in at least a portion of the two-part compositions described herein). In some embodiments, the thiourea is a substituted thiourea, such as a dentally acceptable thiourea. In some embodiments, the thiourea is an organic thiourea, such as a thiourea substituted by an organic radical (such as pyridyl, acetyl, etc.). In a specific embodiment, the thiourea is represented by the structure R ⁶ R ⁷ NC(=S)NR ⁸ R ⁹ , wherein R ⁶ , R ⁷ , R ⁸ and R ⁹ are independently selected from H, COR ¹⁰ , heterocycloalkyl and is selected from heteroaryl (e.g. heterocycloalkyl or heteroaryl is substituted or unsubstituted), and R ¹⁰ is alkyl, heteroalkyl (cyclic or acyclic), aryl or heteroaryl (R ¹⁰ is optionally substituted) not). In specific embodiments, the thiourea group is attached to heterocycloalkyl or heteroaryl at the carbon alpha of the ring heteroatom. In some embodiments, at least one or one of R ⁶ , R ⁷ , R ⁸ and R ⁹ is not H. In specific embodiments, the substituted thiourea is 1-(2-pyridyl)-2-thiourea (PTU), 1-benzoyl-2-thiourea (BTU), 1-acetyl-2-thiourea (ATU) , 1-(2-tetrahydrofurfuryl)-2-thiourea (TTU) and any mixture thereof (i.e. any one or more of PTU, BTU, ATU and/or TTU).

In certain embodiments, the combination of two parts of the composition provided herein results in curing of the composition. In a specific case, the combination of the two parts, especially hydroperoxide and thiourea, promotes the initiation of polymerization of the monomeric components of the composition. In certain embodiments, the inclusion of a copper(II) catalyst accelerates the curing process (e.g., polymerization of the monomer component(s)), resulting in solidification times fast enough to be suitable for dental applications. In some embodiments, when the two-parts are mixed, the mixed composition hardens (e.g., coagulates or solidifies). In one embodiment, the solidification time is achieved without the need for light-curing using a light-curing device that emits primary light having a wavelength in the blue range (e.g., 400 nm to 530 nm, such as about 470 nm). ) is less than 20 minutes. In one embodiment, the clotting time is less than 10 minutes. In one embodiment, the clotting time is less than 5 minutes. In a more preferred embodiment, the cure (e.g., solidification) time is about 250 seconds or less. In a preferred embodiment, the cure (e.g., solidification) time is about 180 seconds or less. In additional or alternative embodiments, the composition has an operating time when the two parts are combined of less than or equal to about 200 seconds, such as less than or equal to about 150 seconds. Additionally, in some embodiments, the operation time is at least 30 seconds (e.g. to enable restoration or filling of dental cavities, especially Class I or Class II cavities).

In certain embodiments, additional additives are included in the composition and/or portions thereof. In some embodiments, any suitable additive is optionally included, such as, but not limited to, photo-initiators, fillers, stabilizers, solvents, or combinations thereof. In a specific embodiment, the dental composition (or portion thereof) includes a resin composition and a filler (e.g., the resin composition includes the materials of the dental composition described herein). In a more specific embodiment, each portion of the composition provided herein includes a resin composition (such as a composition comprising the monomers described herein) and a filler.

In specific embodiments, the compositions (or portions thereof) provided herein include fillers, such as at least one finely divided filler. In some cases, fillings can reduce polarization shrinkage, improve mechanical properties, and increase radiopacity of dental composites. In additional or alternative cases, filling materials may change the rheological properties of the dental composition. Representative fillers include metal oxides, metal nitrides, metal fluorides, silicate glasses, colloidal silica, precipitated silica, fused silica, aluminosilicate glasses, aluminoborosilicate glasses, fluoroaluminosilicate glasses, barium silicate, and barium alumino. Silicates, barium aluminoborosilicate, strontium aluminosilicate, barium fluoro-aluminosilicate, strontium fluoroaluminosilicate, strontium zinc fluoroaluminosilicate, zinc aluminosilicate, pre-polymerized composite filler and one kind thereof Any combination of the above is included, but is not limited thereto. Examples of metal oxides and fluorides include, but are not limited to, barium oxide, strontium fluoride, barium fluoride, ytterbium fluoride, yttrium fluoride, zinc oxide, and bismuth(III) oxide. In one embodiment, the filler is treated with a coupling agent such as γ-methacryloyloxypropyltrimethoxysilane (MPTMS). In some cases, such treatment improves mechanical properties by strengthening the interfacial bond between the filler and the resin matrix.

In some embodiments, the filler is a finely divided filler, such as a filler that includes or consists of a plurality of solid particles. In certain embodiments, the finely divided filler (e.g., particles thereof) has any suitable average dimension, such as, for example, an average size (e.g., particle size) between 0.02 micrometers (μm) and 30 micrometers. In specific embodiments, the average size is between 0.2 micrometers and 10 micrometers.

In certain embodiments, fillers are present in the compositions provided herein in any suitable amount. In some embodiments, filler (such as finely divided filler) is present in the composition in an amount between 10% and 90% by weight. In specific embodiments, the weight percentage is between 40% and 80%.

In certain embodiments, the compositions (or portions thereof) provided herein further include at least one photo-initiator. Any suitable photo-initiator(s) are optionally included. Examples of photo-initiators include benzoin and derivatives, 2,2-diethoxy acetophenone, camphoroquinone, 1-phenyl-1,2-propanedione, monoacylphosphine oxide, bisacylphosphine oxide and the like. Mixtures include, but are not limited to. Additionally, activators can be used in conjunction with photo-initiators. Examples of activators include 2-ethyl-4-(N,N-dimethylamino) benzoate, 2-amyl-4-(N,N-dimethylamino) benzoate, 2-octyl-4-(N,N- dimethylamino) benzoate, 2-(ethylhexyl)-4-(N,N-dimethylamino) benzoate, N,N-dimethylaminoethyl methacrylate, N,N-dimethylaminophenethyl alcohol and mixtures thereof. Included, but not limited to this. In one embodiment, the photo-initiator system comprises camphoroquinone and 2-ethyl-4-(N,N-dimethylamino) benzoate, 2-amyl-4-(N,N-dimethylamino) benzoate, 2- Octyl-4-(N,N-dimethylamino) benzoate, 2-(ethylhexyl)-4-(N,N-dimethylamino) benzoate, N,N-dimethylaminoethyl methacrylate, N,N- and a tertiary amine selected from the group of dimethylaminophenethyl alcohol and any mixtures of one or more thereof. In one embodiment, the weight percentage of photoinitiator is less than 5%. In one embodiment, the weight percentage of photoinitiator is less than 3%.

In certain embodiments, the compositions provided herein include at least one stabilizer. In some embodiments, the stabilizer is an agent that inhibits polymerization of the monomer component(s), such as in the compositions described herein. In certain instances, such agents are useful for improving the shelf life of the compositions provided herein (e.g., to inhibit polymerization of monomers prior to use). Any suitable stabilizer, or polymerization inhibitor (such as a free radical scavenger) is optionally used herein. By way of example, and not limitation, stabilizers include 2,6-di-(tert-butyl)-4-methylphenol (BHT) and 4-methoxyphenol (MEHQ). Any suitable amount of stabilizer, such as less than 1% by weight, is optionally used.

In certain embodiments, provided herein are methods of using and making such compositions, such as in or for dental applications. In a general case, such compositions are prepared in a dentally acceptable manner (i.e. in a manner suitable for administration to the oral cavity (or dental cavity thereof) of an individual, patient or person). In specific embodiments, provided herein are methods of administering compositions described herein to an individual, such as to restore the individual's teeth. In specific embodiments, a composition described herein is provided, any portions thereof are combined to form a mixed composition (e.g., in which case the monomers in the composition are polymerized), and then the mixed composition is administered to the subject (e.g., into the subject's cavity). is administered and the mixed composition is cured (e.g., until coagulated).

In a specific embodiment, the method is used to restore a tooth (e.g., a tooth containing a cavity). In some embodiments, the composition is administered, delivered to and/or used to restore a tooth comprising a Class I or Class II cavity (e.g., based on the G.V. Black classification system), or a cavity of a posterior tooth. do. In certain embodiments, the Class I cavity is located in a pit or fissure of the occlusal surfaces of molars and premolars, the occlusal two-thirds of the buccal surfaces of molars, the lingual surface of the upper incisors, or the lingual surface of the upper molars. It is a vortex that does. In some embodiments, a Class II cavity is a cavity on the basal surface of a molar or premolar. In certain embodiments, the compositions are particularly useful for providing an effective mechanism for filling large cavities - an area where other restorative compositions fall short. In specific embodiments, the cavity treated according to the methods herein is about 3 mm or more (e.g. It has a depth of about 4 mm or more, about 5 mm or more, about 5 mm to about 7 mm, etc.).

In some embodiments, the mixture is further cured, for example by a dental curing light, after it has solidified under intraoral conditions. In additional or alternative embodiments, additional layers of the dental compositions provided herein are placed on top of the coagulated or cured mixture and then cured by a dental curing light.

In specific embodiments, portions of the compositions provided herein are mixed to form a mixed composition, and the mixed composition is administered to a subject (e.g., a dental cavity of the subject) for no longer than 15 minutes (e.g., 0.2 to 15 minutes) under ambient conditions. , 0.5 minutes to 10 minutes, 1 minute to 6 minutes, 2 minutes to 5 minutes, or 3 minutes to 4 minutes, etc.). In specific cases, curing under ambient conditions involves solidifying the composition (e.g., curing in the absence of a photoinitiator device, such as a device that emits light with a predominantly blue wavelength (e.g., in the 400-530 nm range or about 470 nm)). Includes. In specific embodiments, the cured (e.g., self-curing or solidified) composite is further cured using a photoinitiator device, such as a device that emits light having a predominantly blue wavelength (e.g., in the 400-530 nm range or about 470 nm). It hardens with In a more specific embodiment, prior to photo curing, additional admixture composition is administered to the cavity. In some cases, light curing at the surface is desirable to promote complete curing of the filler at the surface (e.g. by allowing radicals - such as those of the living polymer and/or initiator - to interact in the air before completing polymerization/curing). if it can die).

In some embodiments, one or more of the desirable restorative material characteristics described herein are achieved in any suitable manner, such as by using the concentrations of materials described herein. In certain embodiments, provided herein is a composition (e.g., a two-part composition) comprising copper(II) as described herein. In some embodiments, the presence of copper(II) catalyzes hardening (e.g., self-curing) of the composition at a rate sufficient to be effective for dental applications. In some embodiments, the amount of copper(II) (or compounds thereof) present does not need to be high to be effective. For example, in some embodiments, less than 0.1% by weight or even less than 0.01% by weight of copper(II) (or compounds thereof) is used. In additional or alternative embodiments, superior cure rates are achieved using higher hydroperoxide and/or thiourea concentrations. In some embodiments, the compositions provided herein have a combined concentration of hydroperoxides and thioureas (e.g., hydroperoxides and thioureas provided as separate parts of the composition) of about 2.5% by weight (total weight of monomers). Compared - that is, {{weight of hydroperoxide + weight of thiourea} / total weight of monomer} * 100%) or more, about 3% by weight or more, about 4% by weight or more, or about 5% by weight or more.

Provided in certain embodiments herein is a cured combination of the first and second parts of any of the compositions herein, or any composition comprising a hydroperoxide of any composition comprising a thiourea described herein, and It is a dental cement containing a hardened combination of. In certain embodiments, one or both parts of the compositions described herein include a copper(II) catalyst. In some embodiments, the composites provided herein include a cured resin (e.g., comprising polymerized monomer(s) described herein), filler, and copper. In specific embodiments, the composite may comprise the cured resin in any suitable amount, such as an amount described herein relative to the composition comprising the monomer (e.g., from about 10% to about 60% by weight), any suitable amount, such as a filler. filler in an amount described herein (e.g., from about 10 wt.% to about 90 wt.%) relative to the composition comprising, and up to about 1 elemental wt.% (e.g., based on the amount of copper present on an elemental basis) (e.g., about 0.1 wt.%) or less, about 0.05% by weight or less, etc.) of copper. In specific embodiments, the dental composite comprises a filler in an amount of about 60% (w/w) to about 80% (w/w), and an amount of about 20% (w/w) to about 40% (w/w). Contains cured resin.

In certain embodiments, the dental cement compositions provided and used herein have zero to low acid and/or anhydride content. In specific embodiments, the acid and/or anhydride content is less than 5% by weight of the composition. In more specific embodiments, the acid and/or anhydride content is less than 3% by weight of the composition, less than 2% by weight of the composition, less than 1% by weight of the composition, less than 0.5% by weight of the composition, less than 0.1% by weight, etc. In some embodiments, the composition has substantially neutral or alkaline characteristics, such as a pH of at least about 5, a pH of at least about 5.5, a pH of at least about 6, a pH of at least about 6.5, or a pH of at least about 7. In specific examples, it is desirable for the acid content of the composition to be minimized, for any reason such as to minimize moisture sorption or hygroscopicity of the resulting composite. In some cases, when used as a restorative material, high levels of moisture sorption into the composite can result in volume expansion in the restorative material, which can lead to deformation of the restorative material and ultimately build-up of the restorative material, damage to the tooth, and/or It may lead to other undesirable results.

In certain embodiments, the compositions provided herein are cured into a composite with a moisture sorption of about 100 μg/mm ³ or less (or the composites provided herein exhibit such moisture sorption). In specific embodiments, the moisture sorption is less than or equal to about 50 μg/mm ³ , less than or equal to about 25 μg/mm ³ , less than or equal to about 20 μg/mm ³ or less than or equal to about 15 μg/mm ³ .

In some embodiments, composites described herein (such as those formed from a combination of parts of the compositions described herein) have excellent physical parameters for dental applications. In some embodiments, such composites have excellent flexural strength (e.g., greater than 50 MPa, greater than 100 MPa, greater than 125 MPa, etc.). In additional or alternative embodiments, the composite has good compressive strength (e.g., greater than 100 MPa, greater than 150 MPa, greater than 200 MPa, greater than 250 MPa, etc.). In certain embodiments, the composite has excellent diametral strength (e.g., greater than 30 MPa, greater than 40 MPa, greater than 45 MPa, etc.). In some embodiments, the composites provided herein have excellent water solubility (eg, less than 1 μg/mm ³ ). In certain embodiments, the composites provided herein have excellent radiopacity (e.g., greater than 200% Al, greater than 300% AI, etc.). Any suitable method is optionally used to measure such parameters, such as testing films comprising the composite in question (e.g., films having a thickness of about 10 micrometers to about 15 micrometers, such as about 14 micrometers).

Also provided herein are methods of making the compositions described herein. In some embodiments, the component parts of the compositions described herein are combined in any suitable order. Representative procedures are presented in the Examples. In specific embodiments, a portion of the compositions provided herein are prepared by combining monomers, hydroperoxides, optional stabilizers, and optional photoinitiators. In some embodiments, the combination is mixed to form a resin, to which fillers are added and then blended or milled. Likewise, in specific embodiments, a portion of the compositions provided herein are prepared by combining monomers, thioureas, optional stabilizers, and optional photoinitiators. In some embodiments, the combination is mixed to form a resin, to which fillers are added and then blended or milled. Illustrative examples of specific agents (as well as corresponding ingredient class types) as set forth in the Examples are to be understood as being included in the disclosure of the compositions and methods described herein.

Ceramics are inorganic, non-metallic solid materials containing metal, non-metal, or metalloid atoms held primarily by ionic and covalent bonds. In dentistry, ceramic materials have been widely used to fabricate dental crowns; common ceramic materials include, but are not limited to, zirconium oxide, feldspathic porcelain, and lithium disilicate. To achieve good bond strength in these materials, a primer may be required prior to cementation.

Pre-cured dental resins may be used to fabricate crowns, but a primer may be required to create sufficient bond strength.

In some embodiments, the method includes the following steps: 1) applying a dental bonding primer onto the dentin and enamel, optionally followed by applying a cure activator, optionally using a dental curing light to activate the primer. curing the layer; 2) A step of applying a dental bonding primer on prefabricated restoration materials such as crowns, inlays, onlays, and veneers, and optionally subsequently applying a curing activator, and optionally curing the primer layer using dental curing light. step; and 3) bonding the prefabricated restoration to the tooth structure (dentin and enamel) by applying a layer of dental cement.

In some embodiments, the dental bonding primer includes at least one polymerizable monomer having at least one phosphate pendant group. In some embodiments, the monomer is ethylene glycol methacrylate phosphate, bis [2-(methacryloyloxy) ethyl] phosphate, 10-methacryloyloxydecyl dihydrogen phosphate, glycerol phosphate di(meth)acrylate. , Phenyl-P (phenyl methacryloxyethyl phosphate), and PENTA-P (dipentaerythritol pentaacrylate phosphate).

In some embodiments, the dental bonding primer includes at least one polymerizable monomer having at least one carboxylic acid or anhydride pendant group. In some embodiments, the monomer is (meth)acrylic acid, maleic anhydride, trimellitic anhydride, 4-META (4-methacryloxyethyltrimellitic anhydride), maleic anhydride, trimellitic anhydride, 4-META. (4-methacryloxyethyltrimellitic anhydride), PM-HEMA (adduct of pyromellitic anhydride and 2-hydroxyethyl methacrylate), PM-GDM (addition product of pyromellitic anhydride and glycerol dimethacrylate) adduct), BTDA-HEMA (adduct of 3,3',4,4'-benzophenonetetracarboxylic dianhydride and hydroxyethyl methacrylate), and PA-HEMA (adduct of phthalic anhydride and hydroxyethyl methacrylate). adduct of acrylates), MA-GDM (adduct of maleic anhydride and glycerol dimethacrylate).

In some embodiments, the dental bonding primer includes at least one ethylenically unsaturated group with at least one (meth)acrylate group. In a specific embodiment, the ethylenically unsaturated group is selected from acrylate and methacrylate groups. Examples of polymerizable monomers include, but are not limited to: glycerol di(meth)acrylate, glycerol mono(meth)acrylate, hydroxyethyl (meth)acrylate {(meth)acrylate = acrylate or methacrylate}, hydroxypropyl (meth)acrylate, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, octyl (meth)acrylate, decyl (meth)acrylate , 2-ethoxyethyl (meth)acrylate, 2'-ethoxy-2-ethoxyethyl (meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene Glycol di(meth)acrylate, polyethylene glycol mono-(meth)acrylate, polyethylene glycol di-(meth)acrylate, polypropylene glycol mono-(meth)acrylate, polypropylene glycol di-(meth)acrylate, Polytetramethylene glycol mono-(meth)acrylate, polytetramethylene glycol di-(meth)acrylate, hexanediol di(meth)acrylate, octanediol di(meth)acrylate, decanediol di(meth)acrylate , trimethyloylpropane tri(meth)acrylate, urethane dimethacrylate (reaction adduct of 2-hydroxyethyl methacrylate with 2,4,4-trimethylhexane diisocyanate), 2,2-bis[ 4-(2-hydroxy-3-methacryloylpropoxy)-phenyl]-propane (bis-GMA), ethoxylated bisphenol A dimethacrylate in tetrahydrofurfuryl (meth)acrylate (ethylene in molecule The total number of moles of oxides may range from 2 to 30 units) or mixtures thereof. When referred to herein, “(meth)acrylate” includes disclosures of both methacrylates and acrylates.

In some embodiments, the dental bonding primer includes at least one solvent. In some embodiments, the solvent is selected from the group consisting of ethanol, isopropanol, n-propanol, n-butanol, t-butanol, acetone, methyl ethyl ketone, and water.

In some embodiments, the cure activator is a chemical that generates free radicals in an acidic environment.

In some embodiments, the material of the prefabricated restoration is a pre-cured dental resin material that includes at least one inorganic filler. In some embodiments, the material of the prefabricated restoration is ceramic. In some embodiments, the ceramic is selected from the group consisting of zirconium oxide, feldspathic porcelain, and lithium disilicate.

In some embodiments, the dental primer on the prefabricated restoration is a dental bonding agent. In some embodiments, the dental primer is a primer comprising at least one silane having at least one (meth)acrylate pendant group.

In some embodiments, dental cement is delivered onto the prefabricated restoration via a dental double-barrel syringe equipped with a mixing tip.

In some embodiments, excess dental cement is cleaned using a dental instrument. In some embodiments, the dental cement is cured, optionally with a dental curing light.

As used herein, in some cases, “set time” refers to “set time” in the absence of an auxiliary device, such as a dental curing light, specifically designed to promote hardening of restorative materials (e.g., also referred to herein as “self-curing”). The amount of time that a blended composition provided herein (i.e., a composition combining two parts of a two-part composition described herein) forms a solid or rigid composite (partially or fully cured). Dental curing light is a type of dental equipment that uses light-curing resin-based polymer composite materials. It can be used in several different dental materials that are light-curable. The light used belongs to the visible blue light spectrum. This light travels over a range of wavelengths and is variable for each device type. There are four basic dental curing light types: tungsten halogen, light emitting diode (LED), plasma arc curing (PAC), and laser. In certain embodiments, “working time” is the length of time after which the mixed composition ceases to be malleable using conventional dental techniques and/or equipment.

As used herein, weight percentage (% by weight or % (w/w)) refers to the percentage of the weight of a component relative to the overall weight of the composition or composite, unless otherwise noted. In some embodiments, the weight percentage is the weight of the component relative to the weight of the two-part composition (e.g., where the first and second portions are physically separated), and/or the weight of the component relative to the weight of a portion of the two-part composition. refers to the weight of In some cases, the weight percentages of ingredients may be the same or similar in both parts of a two-part system, and in other cases, ingredients may have different weight percentages in each part of the two-part system. For example, in a typical case, the hydroperoxide and thiourea each have different weight percentages in each part, with the hydroperoxide being all or predominant in the first part of the composition and the thiourea in the second part of the composition. Total or mainstream.

The term “alkyl,” when used herein alone or in combination, refers to a saturated, optionally substituted straight chain or optionally substituted branched chain having, for example, 1 to about 10 carbon atoms, more preferably 1 to 6 carbon atoms. Or refers to an unsaturated hydrocarbon monoradical. Examples include methyl, ethyl, n-propyl, isopropyl, 2-methyl-1-propyl, 2-methyl-2-propyl, 2-methyl-1-butyl, 3-methyl-1-butyl, 2-methyl-3. -Butyl, 2,2-dimethyl-1-propyl, 2-methyl-1-pentyl, 3-methyl-1-pentyl, 4-methyl-1-pentyl, 2-methyl-2-pentyl, 3-methyl-2 -pentyl, 4-methyl-2-pentyl, 2,2-dimethyl-1-butyl, 3,3-dimethyl-1-butyl, 2-ethyl-1-butyl, n-butyl, isobutyl, sec-butyl, These include, but are not limited to, t-butyl, n-pentyl, isopentyl, neopentyl, tert-amyl, and hexyl, and longer alkyl groups such as heptyl, octyl, and the like. Whenever it appears herein, a numerical range such as “C ₁ -C ₆ alkyl” means that the alkyl group has, in some embodiments, 1 carbon atom, and in some embodiments, 2 carbon atoms; In some embodiments, 3 carbon atoms; In some embodiments, 4 carbon atoms; In some embodiments, 5 carbon atoms; or in some embodiments, consisting of six carbon atoms, but this definition also covers occurrences of the term “alkyl” where the numerical range is not specified. Additionally, in some cases, such as when alkyl is substituted on both sides (e.g. as shown above for L), alkyl may refer to a diradical derived from the above-defined monoradical alkyl. Examples include methylene (-CH ₂ -), ethylene (-CH ₂ CH ₂ -), propylene (-CH ₂ CH ₂ CH ₂ -), isopropylene (-CH(CH ₃ )CH ₂ -), etc. It is not limited to this. “Alkyl” is an optionally substituted alkyl group containing, for example, 3 to about 15 ring carbon atoms or 3 to about 10 ring carbon atoms and, in some embodiments, additional non-ring carbon atoms as substituents (e.g., methylcyclopropyl). It may also refer to a cyclic alkyl group, which refers to a saturated hydrocarbon monoradical ring. The terms include fused, non-fused, bridging and spiro radicals. In some embodiments, the fused cycloalkyl contains 2 to 4 fused rings, where the bonding ring is a cycloalkyl ring. Examples include, but are not limited to, cyclopropyl, cyclopentyl, cyclohexyl, cumene, and pinan ring systems.

The term “aryl,” when used herein alone or in combination, refers to an optionally substituted aromatic hydrocarbon radical of 6 to about 20 ring carbon atoms and includes fused and non-fused aryl rings. A fused aryl ring radical contains 2 to 4 fused rings, where the ring of bonds is an aryl ring and the other individual rings are cycloaliphatic, heterocyclic, aromatic, heteroaromatic, or any combination thereof. The term aryl also includes fused and non-fused rings containing from 6 to about 12 ring carbon atoms, as well as those containing from 6 to about 10 ring carbon atoms. Non-limiting examples of single ring aryl groups include phenyl; Fused ring aryl groups include naphthyl, phenanthrenyl, anthracenyl, azulenyl; Non-fused 2-aryl groups include biphenyl.

The term "heteroaryl," when used herein alone or in combination, refers to a heteroatom containing from about 5 to about 20 skeletal ring atoms, wherein one or more of the ring atoms are independently selected from, but are not limited to, oxygen, nitrogen, and sulfur. refers to an optionally substituted aromatic monoradical, provided that the ring of the group does not contain two adjacent O or S atoms. In embodiments in which two or more heteroatoms are present in the ring, each of the two or more heteroatoms is identical to each other, or some or all of the two or more heteroatoms are different from each other. The term heteroaryl includes optionally substituted fused and non-fused heteroaryl radicals having at least one heteroatom. The term heteroaryl also includes fused and non-fused heteroaryls having 5 to about 12 skeletal ring atoms, as well as those having 5 to about 10 skeletal ring atoms. In certain cases, the bond to a heteroaryl group is through a carbon atom or heteroatom. Non-limiting examples of single ring heteroaryl groups include pyridyl or furanyl.

As used herein, the term "heteroalkyl" means that one or more of the backbone chain carbon atoms (and, if applicable, any attached hydrogen atoms) are each independently heteroatoms (i.e. atoms other than carbon, such as, but not limited to, However, it refers to an optionally substituted alkyl structure as described above that has been replaced by oxygen, nitrogen, sulfur, or combinations thereof. Representative heteroalkyl groups include straight chain groups such as ethylene oxide (such as -CH2CH2On-) or cyclized groups such as tetrahydrofuran.

[ Example ]

Abbreviations of materials used in the examples include:

PTU: 1-(2-pyridyl)-2-thiourea

CHP: Cumene hydroperoxide

CuPD: Copper(II) acetylacetonate

MDP: 10-methacryloyloxydecyl dihydrogen phosphate

R202: AEROSIL® Fumed Silica

R812S: Aerosil® Fumed Silica

GM27884-K6: Schott GM27884 dental glass, 3 ㎛

YbF3: Ytterbium fluoride

BYK W9010: Wetting and dispersing additive (rheology modifier)

CQ: camphorquinone

EDMAB: Ethyl-4-dimethylamino benzoate

UDMA: Urethane dimethacrylate

E6BAD: Ethoxylated (6) bisphenol A dimethacrylate

EBPADM: Ethoxylated (3) Bisphenol A Dimethacrylate

BisGMA: Bisphenol A-glycidyl methacrylate

TEGDM: Triethylene glycol dimethacrylate

BHT: Butylated hydroxytoluene

HDK N-20P: Fumed Silica

Pluronic L-44: Surfactant

DI water: distilled water

DHEPT: N-N-bis(2-hydroxyethyl)-p-toluidine

BPO: Benzoyl peroxide

Example One - 16% MDP Preparation of binder comprising

Examples 1 and 2 were prepared by adding and mixing chemicals. All chemicals were mixed until all solids except the fumed silica were dissolved, resulting in a low viscosity liquid.

Example 2 - 8 % MDP and 8 % PMDM Preparation of binder comprising

Example 2 was prepared by mixing Examples 1 and 2 in proportion.

Comparative example A -- 0 % MDP and 16% PMDM Preparation of binder comprising

Examples 1 and 2 were prepared by adding and mixing chemicals. All chemicals were mixed until all solids except the fumed silica were dissolved, resulting in a low viscosity liquid.

Example 3 - part 1 CHP - co-initiator -contain of paste manufacturing

Example 3 was prepared by adding and mixing chemicals. The resin chemistry was mixed with soluble solids including CQ, EDMAB and BHT until all solids were dissolved. Next, solid fillers including R812S, YbF3 and GM27884 were added and mixed by a speed mixer and then by a 3-roll mill to produce a paste-like semi-solid.

Example 4 - second part PTU - co-initiator -contain of paste manufacturing

Example 4 was prepared by adding and mixing chemicals. The resin chemistry was mixed with soluble solids including CQ, EDMAB, PTU and BHT until all solids were dissolved. CuPD was added to the mixer of TEGDMA and mixed by speed mixer. Next, solid fillers including R812S, YbF3 and GM27884 were added and mixed by a speed mixer and then by a 3-roll mill to produce a paste-like semi-solid.

Example 5 - part 1 Example 3 paste and second part Example 4 paste Preparation of mixture

Implemented by filling Examples 3 (CHP-coinitiator-containing) and 4 (PTU-coinitiator-containing) into a double-barrel syringe, each barrel containing one of the respective pastes as a first part and a second part. Example 5 was prepared. When such a paste combination is used, a mixing tip is provided to ensure proper mixing of the two pastes by passing them through the mixing chamber. Upon mixing, the material is allowed to cure over a time period of approximately 4 to 8 minutes.

Example 7 and 8 and Comparative example B - binder and mixed first and second part cement paste Application of

The zirconia substrate was embedded in a polymer resin and the top layer was cut away and exposed. After exposing the substrate, it was polished with 600 grit SiC paper. The zirconia surface was further sandblasted using 50 nm aluminum oxide powder at a pressure of 60 psi. Next, all specimens were thoroughly cleaned. A light brushing operation was applied to the binder layer of either Example 1 or 2 or Comparative Example A, followed by air thinning for approximately 10 seconds. Next, the specimen was placed in a joining jig as described in ISO 29022-2013. The paste mixture of Example 5 was injected into the cavity and kept in a 35° C. humidity chamber for 1 hour before being removed from the jig. Next, the specimen was placed in water and kept in an oven at 37°C for 20 hours. Next, the bond strength of the specimens was recorded according to ISO 29022-2013. Using 10 specimens from each group, the average bond strength and standard deviation were reported in Table 1 below. The results show that the MDP containing binders provide bond strengths exceeding 15 MPa at both 16% (Example 1) or 8% (Example 2) at 19.8 MPa and 19.1 MPa respectively; The binder of Comparative Example A, which lacks MDP, has a low bonding strength of 11.6 MPa, less than 15 MPa.

Comparative example C - part 1 BPO - co-initiator -contain of paste manufacturing

Comparative Example C was prepared by adding and mixing chemicals as performed in Example 3. The resin chemistry was mixed with soluble solids including CQ, EDMAB, BPO and BHT until all solids were dissolved. Next, solid fillers including R812S, YbF3 and GM27884 were added and mixed by a speed mixer and then by a 3-roll mill to produce a paste-like semi-solid.

Comparative example D - second part DHEPT - co-initiator -contain of paste manufacturing

Comparative Example D was prepared by adding and mixing chemicals as performed in Example 4. The resin chemistry was mixed with soluble solids including CQ, EDMAB, DHEPT and BHT until all solids were dissolved. Next, solid fillers including R812S, YbF3 and GM27884 were added and mixed by a speed mixer and then by a 3-roll mill to produce a paste-like semi-solid.

Comparative example E - part 1 Example C paste and second part Example D paste Preparation of mixture

Comparative Example E was prepared as performed in Example 5 by filling Comparative Examples C and D into a double-barrel syringe where each barrel holds one paste. When such a paste combination is used, a mixing tip is provided so that proper mixing can be achieved by passing the two pastes through a mixing chamber. Upon mixing, the material is allowed to cure over a time period of approximately 4 to 8 minutes.

Comparative example F and G - binder and mixed first and second part cement of paste apply

As performed in Examples 7 and 8, the zirconia substrate was embedded in a polymer resin and the top layer was cut away and exposed. After exposing the substrate, it was polished with 600 grit SiC paper. The zirconia surface was further sandblasted using 50 nm aluminum oxide powder at a pressure of 60 psi. Next, all specimens were thoroughly cleaned. A light brushing operation was applied to the layer of Example 1 or 2, followed by air thinning for about 10 seconds. Next, the specimen was placed in a joining jig as described in ISO 29022-2013. The paste mixture of Comparative Example E was injected into the cavity, kept in a 35° C. humidity chamber for 1 hour, and then removed from the jig. Next, the specimen was placed in water and kept in an oven at 37°C for 20 hours. Next, the bond strength of the specimens was recorded according to ISO 29022-2013. Using 10 specimens from each group, the average bond strength and standard deviation were reported in Table 2 below. The results shown in Table 2 are 19.8 MPa and 19.1 MPa, respectively, compared to BPO (Example C) when CHP (Example 3) and PTU (Example 4) were used as co-initiators in the first and second parts. and when DHEPT (Example D) was used as a co-initiator in the first and second part co-initiator-containing pastes for preparing the cement paste, the bond strengths were much lower and weaker at 8.1 MPa and 11.4 MPa. It is showing.

Claims (22)

binder; and
A paste mixture formed by mixing together a previously separate first portion and a second portion, wherein the first portion comprises at least one polymerizable monomer and at least one hydroperoxide, wherein the hydroperoxide is cumene. hydroperoxide (CHP), wherein the second part comprises at least one thiourea compound, wherein the thiourea is 1-(2-pyridyl)-2-thiourea (PTU).
A dental composition comprising on the surface of a dental substrate,
wherein the binder comprises 8% to 16% of 10-methacryloyloxydecyl dihydrogen phosphate (10-MDP), and the first or second portion of the paste mixture further comprises a copper(II) compound. , a dental composition wherein the bonding strength of the binder on the dental substrate exceeds 15 MPa. The dental composition according to claim 1, wherein the dental substrate is zirconia. The dental composition according to claim 1, wherein the bonding agent is a single bottle bonding agent. As a first step of applying a bonding agent to a dental substrate, the bonding agent includes at least one phosphoric acid-containing (meth)acrylic monomer, wherein the phosphoric acid-containing (meth)acrylic monomer is 10-methacryloyloxydecyl dihydrogen. The first step is phosphate (10-MDP); and
A second step of applying the paste mixture from a device comprising a first part and a second part that are separate from each other,
the first portion and the second portion form a paste mixture,
The paste mixture from the device comprises at least one polymerizable monomer and at least one hydroperoxide in the first part, wherein the hydroperoxide is cumene hydroperoxide (CHP), and in the second part A second step comprising at least one thiourea compound, wherein the thiourea is 1-(2-pyridyl)-2-thiourea (PTU)
A dental composition for use in a tooth restoration method comprising,
A dental composition, wherein the first part or the second part of the paste mixture further comprises a copper(II) compound, and the bonding strength of the binder on the dental substrate is greater than 15 MPa. The dental composition according to claim 4, wherein the binder effectively binds to the dental substrate. The dental composition according to claim 4, wherein the dental substrate is zirconia. 5. The dental composition of claim 4, wherein the device is a double-barrel syringe. 2. The dental composition of claim 1, wherein the previously separate first and second portions were separated in a double-barrel syringe. delete delete delete delete delete delete delete delete delete delete delete delete delete delete